Merocyanine derivatives

ABSTRACT

Disclosed is the use of merocyanine derivatives of formula 
     
       
         
         
             
             
         
       
         
         Q is hydrogen; C 1 -C 22 alkyl; —OH; —OR 7 ; —NR 7 R 8 ; or —N═R 9 ; 
         R 1  is hydrogen; C 1 -C 22 alkyl; —OR 7 , —SR 7 ; —NR 7 R 8 ; C 1 -C 22 alkyl; C 2 -C 12  alkenyl; C 2 -C 12 alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 12 aralkyl; C 1 -C 12 heteroalkyl, C 2 -C 11 heteroaralkyl; C 6 -C 10 aryl; or C 1 -C 9 heteroaryl; 
         R 4  is cyano; COR 7 , COOR 7 ; CONR 7 R 8 ; SO 2 (C 6 -C 12 )aryl; C 2 -C 12 alk-1-enyl; C 3 -C 12 cycloalk-1-enyl; C 2 -C 12 alk-1-inyl; C 2 -C 12 heteroalkyl; C 3 -C 5 heterocycloalkyl; C 6 -C 10 aryl; or C 1 -C 9 heteroaryl; 
         R 5  is —COR 7 ; —COOR 7 ; —OR 7 ; —SR 7 , —NHR 7 , —NR 7 R 8 ; C 1 -C 22 alkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 12 aralkyl; C 1 -C 12 alkylphenyl; C 1 -C 12 alkoxy-C 6 -C 10 aryl; C 1 -C 12 heteroalkyl; C 2 -C 11 heteroaralkyl; C 3 -C 12 cycloheteroalkyl; C 6 -C 10 aryl; C 1 -C 12 alkoxy-C 6 -C 10 aryl; or C 1 -C 9 heteroaryl; 
         R 6  is hydrogen; C 1 -C 22 alkyl; C 1 -C 22 alkoxy; or COR 7 ; 
         R 7  and R 8  independently from each other are hydrogen; C 1 -C 22 alkyl; C 2 -C 12 alkenyl; C 2 -C 12 alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; —(CH 2 ) t COOH; C 7 -C 12 aralkyl; C 1 -C 12 heteroalkyl; C 2 -C 11 heteroaralkyl; C 6 -C 10 aryl; C 1 -C 9 heteroaryl; Si—R 10 R 11 R 12 ; Si(OR 10 )(OR 11 )(OR 12 ); SiR 10 (OR 11 )(OR 12 ); SiR 10 R 11 (OR 12 ); —(CH 2 ) u —O—(CH 2 ) v —SiR 10 R 11 R 12 ; or a radical X-Sil; 
         t, u and v, independently from each other are a number from 1 to 5; 
         R 9  is a (C 1 -C 6 )alkylidene radical; 
         R 10 , R 11 , R 12  independently form each other are C 1 -C 22 alkyl; 
         X is a linker;
 
for protecting of human hair and skin against the damaging effect of UV radiation.

This application is a divisional of application Ser. No. 11/630,489, filed on Dec. 21, 2006, pending, which is a 371 of international app. No. PCT/EP05/52850, filed Jun. 20, 2005, which claims priority to EP 04103018.0, filed Jun. 29, 2004, all of which are herein incorporated by reference.

The present invention relates to the use of the compounds of formula

wherein

-   Q is hydrogen; C₁-C₂₂alkyl; —OH; —OR₇; —NR₇R₈; or —N═R₉; -   R₁ is hydrogen; C₁-C₂₂alkyl; —OR₇, —SR₇; —NR₇R₈; C₁-C₂₂alkyl; C₂-C₁₂     alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂aralkyl; C₁-C₁₂heteroalkyl, C₂-C₁₁heteroaralkyl; C₆-C₁₀aryl;     or C₁-C₉heteroaryl; -   R₄ is cyano; COR₇, COOR₇; CONR₇R₈; SO₂(C₆-C₁₂)aryl;     C₂-C₁₂alk-1-enyl; C₃-C₁₂cycloalk-1-enyl; C₂-C₁₂heteroalkyl;     C₃-C₅heterocycloalkyl; C₆-C₁₀aryl; or C₁-C₉heteroaryl; -   R₅ is —COR₇; —COOR₇; —OR₇; —SR₇, —NHR₇, —NR₇R₈; C₁-C₂₂alkyl;     C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂aralkyl; C₁-C₁₂alkylphenyl; C₁-C₁₂alkoxy-C₆-C₁₀aryl;     C₁-C₁₂heteroalkyl; C₂-C₁₁heteroaralkyl; C₃-C₁₂cycloheteroalkyl;     C₆-C₁₀aryl; C₁-C₁₂alkoxy-C₆-C₁₀aryl; or C₁-C₉heteroaryl; -   R₆ is hydrogen; C₁-C₂₂alkyl; C₁-C₂₂alkoxy; or COR₇; -   R₇ and R₈ independently from each other are hydrogen; C₁-C₂₂alkyl;     C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     —(CH₂)_(t)COOH; C₇-C₁₂aralkyl; C₁-C₁₂heteroalkyl;     C₂-C₁₁heteroaralkyl; C₆-C₁₀aryl; C₁-C₉heteroaryl; Si—R₁₀R₁₁R₁₂;     Si(OR₁₀)(OR₁₁)(OR₁₂); SiR₁₀(OR₁₁)(OR₁₂); SiR₁₀R₁₁(OR₁₂);     —(CH₂)_(u)—O—(CH₂)_(v)—SiR₁₀R₁₁R₁₂; or a radical X-Sil; -   t, u and v, independently from each other are a number from 1 to 5; -   R₉ is a (C₁-C₆)alkylidene radical; -   R₁₀, R₁₁, R₁₂ independently form each other are C₁-C₂₂alkyl; -   X is a linker; -   Sil is a silane-, oligosiloxane- or polysiloxane radical; -   R₁ and R₂, R₁ and Q, R₁ and R₆, R₁ and T, R₂ and R₃, R₂ and R₄, R₂     and R₆, R₂ and Q, R₄ and R₆, R₄ and T, R₆ and Q, T and Q, each     independently, are linked together, so that 1, 2, 3 or 4 carbocyclic     or N, O and/or S-heterocyclic rings are formed, wherein each of     them, independently from each other, may be condensed with an     aromatic or heteroaromatic ring, and/or more N—, O- and/or     S-heterocyclic rings, and each N atom in a N-heterocyclic ring may     be substituted by C₁-C₂₂alkyl; -   n is a number from 1 to 4; wherein at least one of the radicals R₁,     R₆ or Q is different from hydrogen; -   if n=1 -   T is —COR₅; —CN; C₆-C₁₀aryl; —NHR₅; or —SO₂—(C₆-C₁₂)aryl; -   R₂ and R₃ independently from each other are C₁-C₂₂alkyl;     hydroxy-C₁-C₂₂alkyl; C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl,     C₃-C₁₂cycloalkenyl; C₇-C₁₂ aralkyl; C₁-C₁₂heteroalkyl;     C₃-C₁₂cycloheteroalkyl; C₆-C₁₀aryl; C₁-C₉heteroaryl; or a radical of     formula

-   p is a number from 5 to 100 -   q is a number from 1 to 5; -   s is a number from 0 to 4; -   if n 2 -   R₂ and R₃ are each C₁-C₅alkylene; and simultaneously T is defined as     for n=1; or -   T is a bivalent radical of formula —NR₇—V—NR₇—, wherein -   V is phenylene; or C₁-C₅alkylene; -   R₇ is hydrogen; or C₁-C₅alkyl; and R₂ and R₃ simultaneously are     defined as for n=1; -   if n=3 -   one of R₂, R₃ or T is a trivalent radical; -   if n=4 -   one of R₂, R₃ or T is a tetravalent radical;     for protecting of human hair and skin against the damaging effect of     UV radiation.

Halogen ist chloro, bromo, fluoro or Iodo, preferably chloro.

Alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl may be straight chained or branched, monocyclic or polycyclic.

Alkyl ist for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl or dodecyl.

Alkenyl is for example straight-chain C₂-C₁₂alkenyl or preferably branched C₃-C₁₂alkenyl. C₁-C₁₂alkyl, like vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl oder die verschiedenen isomeren von hexenyl, octenyl, nonenyl, decenyl oder dodecenyl.

C₃-C₁₂cycloalkyl is for example cyciopropyl, cyclobutyl, cyclopentyl, trimethylcyclohexyl or preferably cyclohexyl.

C₇-C₁₈aralkyl is for example benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, 9-fluorenyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl oder 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl.

(C₁-C₆)alkylidene is for example methylene, ethyl-1-ene, propyl-2-ene. C₆-C₁₄ayrl is for example phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or terphenylyl.

C₁-C₁₂heteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated π-electrons, for example 2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl, tetrazolyl or another ring system from thiophene-, furan-, pyridine, thiazol, oxazol, imidazol, isothiazol, triazol, pyridine- and benzene rings, which are unsubstituted or substituted by 1 to 6 ethyl, methyl, ethylene and/or methylene, like benzotriazolyl, bei N-heterocycles optionally in the form of their N-oxides.

C₂-C₁₆heteroaralkyl is for example C₁-C₈alkyl substituted with C₁-C₈heteroaryl.

Preferably compounds of formula (1) are used, wherein

-   Q is —OH; —OR₇; —NR₇R₈; or —N═R₉; -   T is —COR₅; —CN; or —SO₂—(C₆-C₁₂)aryl; -   R₁ is hydrogen; —OR₇, —SR₇; —NR₇R₈; C₁-C₂₂alkyl; C₂-C₁₂alkenyl;     C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; C₇-C₁₂aralkyl;     C₁-C₁₂heteroalkyl; C₂-C₁₁heteroaralkyl; C₆-C₁₀aryl; or     C₁-C₉heteroaryl; -   R₂ and R₃ independently from each other are C₁-C₂₂alkyl;     C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl;     C₇-C₁₂ aralkyl; C₁-C₁₂heteroalkyl; C₃-C₁₂cycloheteroalkyl;     C₂-C₁₁heteroaralkyl, C₆-C₁₀aryl; or C₁-C₉heteroaryl; -   R₄ is cyano; COR₇, COOR₇; CONR₇R₈; SO₂(C₆-C₁₂)aryl,     C₂-C₁₂alk-1-enyl; C₃-C₁₂cycloalk-1-enyl; C₂-C₁₂alk-1-inyl;     C₂-C₁₂heteroalkyl, C₃-C₅heterocycloalkyl, C₆-C₁₀aryl; or     C₁-C₉heteroaryl; -   R₅ is —COR₇; —COOR₇; —OR₇; —SR₇; —NR₇R₈; C₁-C₂₂alkyl; C₂-C₁₂alkenyl;     C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; C₇-C₁₂aralkyl;     C₁-C₁₂alkylphenyl; C₁-C₁₂alkoxy-C₆-C₁₀aryl; C₁-C₁₂heteroalkyl;     C₂-C₁₁heteroaralkyl; C₃-C₁₂cycloheteroalkyl; C₆-C₁₀aryl;     C₁-C₁₂alkoxy-C₆-C₁₀aryl or C₁-C₉heteroaryl; -   R₆ is C₁-C₂₂alkyl; C₁-C₂₂alkoxy; or COR₇; -   R₇ and R₈ independently from each other are hydrogen; C₁-C₂₂alkyl;     C₂-C₁₂alkenyl, C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂aralkyl; C₁-C₁₂heteroalkyl; C₂-C₁₁heteroaralkyl; C₆-C₁₀aryl;     o-C₆-C₁₀aryl; or C₁-C₉heteroaryl; -   R₉ is a (C₁-C₆)alkylidene radical; or -   R₁ and R₂, R₁ and Q, R₁ and R₄, R₁ and R₆, R₂ and R₃, R₃ and Q, R₆     and Q, T and Q, each independently, are linked together, so that 1,     2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are     formed, wherein each of them, independently from each other, may be     condensed with an aromatic or heteroaromatic ring, and/or more N—,     O- and/or S-heterocycic rings, and each N atom in a N-heterocyclic     ring may be substituted by C₁-C₂₂alkyl; and -   n is 1.

More preferred is the use of the compounds of formula (1), wherein

-   Q is —OH; —OR₆; or —NR₇R₈; -   T is —COR₅—CN; or —SO₂—(C₆-C₁₂)aryl; -   R₁ is hydrogen; —OR₇, —SR₇; —NR₇R₈; C₁-C₂₂alkyl; C₂-C₁₂alkenyl;     C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; C₇-C₁₂aralkyl;     or C₆-C₁₀aryl; -   R₂ and R₃ independently from each other are C₁-C₂₂alkyl;     C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂ aralkyl; or C₆-C₁₀aryl; -   R₄ is cyano; —COR₅, —COOR₇; —CONR₇R₈; —SO₂(C₆-C₁₂)aryl;     —C₁-C₂₂alkylcarbonylamino-C₆-C₁₀aryl; or C₆-C₁₀aryl; -   R₅ is —COR₇; —COOR₇; —CONR₇R₈, —OR₇, —SR₇, —NR₇R₈, C₁-C₂₂alkyl;     C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂aralkyl; C₆-C₁₀aryl; or C₁-C₁₂alkoxy-C₆-C₁₀aryl; -   R₆, R₇ and R₈ independently from each other are hydrogen;     C₁-C₂₂alkyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; C₇-C₁₂aralkyl; or     C₆-C₁₀aryl; or -   R₁ and R₂, R₁ and Q, R₁ and R₄, R₁ and R₆, R₂ and R₃, R₃ and Q, R₆     and Q, T and Q are linked together pairwise, so that 1, 2, 3 or 4     carbocyclic or N—, O- and/or S-heterocyclic rings are formed,     wherein each of them, independently from each other may be condensed     with an aromatic or heteroaromatic ring, and/or more N, O and/or     S-heterocycic rings, and each N atom in a N-heterocyclic ring may be     substituted by C₁-C₂₂alkyl.

Even more preferred is the use of the compounds of formula (1), wherein

-   R₁ is hydrogen; —S—C₁-C₂₂alkyl; or R₁ and R₂, or R₁ and R₄ together     with the linking nitrogen atom form an alkylene radical which my be     interrupted by one or more —O— and/or —NR₇— or may be condensed with     an aromatic ring; and -   R₇ is C₁-C₂₂alkyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂aralkyl; or C₆-C₁₀aryl.

Most preferred is the use of the compounds of formula (1), wherein

-   R₁ is hydrogen.

Furthermore, the use of compounds formula (1) is preferred, wherein

-   R₂ and R₃ independently from each other are C₁-C₅alkyl;     phenyl-C₁-C₃alkyl; hydroxy-C₁-C₁₂alkyl; or R₂ and R₃, or R₂ and R₄,     or R₂ and Q together with the linking nitrogen atom form an alkylene     radical which my be interrupted by one or more —O— and/or —NR₇— or     may be condensed with an aromatic ring; and -   R₇ is C₁-C₂₂alkyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl;     C₇-C₁₂aralkyl; or C₆-C₁₀aryl;

And most preferably the use of the compounds of formula (1), wherein

-   R₂ and R₃ independently from each other are C₁-C₅alkyl; or R₂ and R₃     together with the linking nitrogen atom form a C₂-C₄alkylene radical     which may be interrupted by ±0- or —NR₇; and -   R₇ is hydrogen; or C₁-C₅alkyl.

Preferred is also the use of compounds of formula (1), wherein

-   R₄ is —COR₅; phenyl, which is optionally substituted by C₁-C₅alkyl;     —CN; or —SO₂—(C₆-C₁₀)aryl; or -   R₄ and T together with a bivalent C₃-C₇alkylene radical which my be     interrupted by one or more —O— and/or —NR₇— form a carbocyclic ring     which may be condensed with an aromatic ring; and -   R₇ is hydrogen; or C₁-C₅alkyl.

Furthermore the use of compounds of formula (1) is preferred, wherein

-   R₄ is —CN; or COR₅; -   R₅ is C₁-C₁₂alkyl; or C₁-C₁₂alkoxy; or -   R₄ and T together with the bivalent radical of the formula

wherein

-   U₁ and U₃ independently from each other are a radical of formula     —CHR₇; —NHR₇—; or —O—; -   U₂ is —CH₂; or —CO—; or the direct bond; -   R₇ is hydrogen; or C₁-C₁₂alkyl; form an aromatic ring.

Most preferred is the use of compounds of formula (1), wherein

-   T and R₄ together with the bivalent radicals selected from

form a heterocyclic ring.

Furthermore, the use of compounds of formula (1) is preferred, wherein

-   R₆ is hydrogen; C₁-C₅alkyl; C₁-C₅alkoxy; —O—(C₆-C₁₀aryl); or -   R₆ and Q together with a bivalent C₃-C₇alkylene radical which may be     interrupted by one or more —O— and/or —NR₇— or may be condensed with     an aromatic ring, form a heterocyclic ring; and -   R₇ is hydrogen; or C₁C₁₂alkyl; and most preferably wherein -   R₆ is hydrogen.

Furthermore, the use of compounds ofse according to any of formula (1) is preferred, wherein

-   T is —CN; —COR₅; or —SO₂-phenyl; -   R₅ is C₁-C₅alkyl; C₁-C₅alkoxy; or NR₇R₈; -   R₇ and R₈ independently from each other are hydrogen; or C₁-C₅alkyl;     or -   T and Q together with the bivalent C₃-C₇alkylene radical which may     be interrupted by one or more —O— and/or —NR₇— or may be condensed     with an aromatic ring, form a heterocyclic ring; and most preferably     the use of compounds of formula (1), wherein -   T is —CN; or —COR₅; and -   R₅ is C₁-C₅alkyl; or C₁-C₅alkoxy.

Furthermore, the use of compounds of formula (1) is preferred, wherein

-   Q is hydroxy; C₁-C₅alkoxy; or —NR₇R₈; and -   R₇ and R₈ independently from each other are hydrogen; C₁-C₅alkyl; or     phenyl, which may be substituted by one or more C₁-C₅alkyl or     C₁-C₅alkoxy groups; and most preferably, wherein -   Q is hydroxy.

Furthermore, the use of compounds of formula

is preferred, wherein

-   U₄, U₅, U₆, U₇ and U₈ independently of each other are —CHR₅—; —CO—;     —NR₇—; —CS—; or —O—; -   R₅ is hydrogen; or C₁-C₅alkyl; and -   R₁, R₂, R₃, R₆, R₇ and Q are defined as in formula (1).

Furthermore, the use of compounds of formula

is preferred, wherein

-   R₆ is hydrogen; or C₁-C₅alkyl; and -   R₃, R₄, and T are defined as in formula (1); more preferably,     wherein -   R₃ is C₁-C₂₂alkyl; C₆-C₁₀aryl; or C₇-C₁₂aralkyl; and most     preferably, wherein -   R₃ is C₆-C₁₀aryl.

Furthermore, the use of compounds of formula (1) is preferred, wherein at least one of the radicals R₁, R₆ or Q is different from hydrogen.

Preferred is also the use of compounds of formula (1), wherein

-   Q is hydrogen; or C₁-C₂₂alkyl; -   T is —COR₅; —CN; or —SO₂—(C₆-C₁₂)aryl; -   R₁ is hydrogen; or C₁-C₂₂alkyl; -   R₂ and R₃ independently from each other are C₁-C₂₂alkyl; -   R₄ is CN; COR₅; CONH₂; or SO₂(C₆-C₁₂)aryl, -   R₅ is —OR₇; —SR₇, —NHR₇, —NR₇R₈; C₁-C₂₂alkyl; C₇-C₁₂aralkyl; -   R₇ and R₈ independently from each other are hydrogen; C₁-C₂₂alkyl;     —(CH)_(m)—Si—R₁₀R₁₁R₁₂; Si(OR₁₀)(OR₁₁)(OR₁₂); SiR₁₀(OR₁₁)(OR₁₂);     SiR₁₀R₁₁(OR₁₂), or a radical X-Sil; -   R₉ is a (C₁-C₆)alkylidene radical; -   R₁₀, R₁₁, R₁₂ independently form each other are C₁-C₂₂alkyl; -   X is a linker; -   Sil is a silane-, oligosiloxane- or polysiloxane radical; -   R₁ and R₂, R₁ and Q, R₁ and R₆, R₁ and T, R₂ and R₃, R₂ and R₄, R₂     and R₆, R₂ and Q, R₄ and R₆, R₄ and T, R₆ and Q, T and Q, each     independently, are linked together, so that 1, 2, 3 or 4 carbocyclic     or N, O and/or S-heterocyclic rings are formed, wherein each of     them, independently from each other, may be condensed with an     aromatic or heteroaromatic ring, and/or more N—, O- and/or     S-heterocycic rings, and each N atom in a N-heterocyclic ring may be     substituted by C₁-C₂₂alkyl; -   n is anumber from 1 to 4; and -   m is a number for 0 to 4; wherein at least one of the radicals R₁,     R₆ or Q is different from hydrogen;

Preferred is the use of compounds of formula (1), wherein

-   R₁, R₆ and Q, independently from each other are hydrogen; or     C₁-C₂₂alkyl, wherein at least one of R₁, R₆ and Q is different from     hydrogen; and most preferrd the use of compounds of formula (1),     wherein -   R₁, R₆ and Q, independently from each other are hydrogen; or     C₁-C₅alkyl, wherein at least one of R₁, R₆ and Q is different from     hydrogen.

Preferred is also the use according of compounds of formula (1), wherein

-   T and R₄ independently from each other are —COR₅; —CN; or     —SO₂—(C₆-C₁₂)aryl; and -   R₅ is —OR₇; —NR₇R₆; C₁-C₂₂alkyl; C₇-C₁₂aralkyl; -   R₇ and R₈ independently from each other are hydrogen; C₁-C₂₂alkyl;     —(CH₂)_(m)—Si—R₁₀R₁₁R₁₂; and -   R₁₀, R₁₁, and R₁₂ independently from each other are C₁-C₂₂alkyl.

Most preferred is the use of compounds of formula (1), wherein

-   T and R₄ independently from each other are —CN; SO₂C₆H₅;

or a radical of formula

wherein

-   R₇ and R₉, independently from each other are C₁-C₁₂alkyl; or a     radical of formula —SiR₁₀R₁₁R₁₂; and -   R₁₀, R₁₁ and R₁₂ are C₁-C₅alkyl.

Furthermore the present invention relates to the use of monomeric and polymeric compounds having the structural element of formula

wherein at least one of the asterix-marked radicals are joint with the monomeric or polymeric radical; and R₁, R₂, R₄ and R₆ are defined as in formula (1).

Examples of merocyanine derivatives used in the present invention are listed in Table 1:

TABLE MC2a

R₂ R₃ Q R₆ R₁ T R₄ MC01 i-propyl i-propyl OH H H

MC02 λ_(max) = 374 nm CH₃ CH₃ OH H H

MC03 λ_(max) = 375 nm CH₃ CH₃ OH H H

MC04 λ_(max) = 363 nm CH₃ CH₃ OH H H

MC05 λ_(max) = 371 nm R₂ + R₁

CH₃ OH H —

MC06 λ_(max) = 384 nm CH₃ CH₃ OH H H

MC07

OH H H

MC08 CH₃ n-butyl OH H H

MC09 CH₃ CH₃ OH H

MC10 CH₃ CH₃ OH

—CN —(CO)—CH₃ MC11 CH₃ CH₃ OH H H

MC12

OH H H

MC13 R₂ = R₁ CH₃ OH H — —(CO)N(C₂H₅)₂ —(CO)—CH₃

MC14 CH₃ CH₃ OH

—(CO)—CH₃ MC15

OH H H

MC16 λ_(max) = 399 nm CH₃ CH₃ OH H H

MC17 λ_(max) = 373 nm CH₃ i-propyl OH H H

MC18 i-propyl i-propyl OH H H

MC19 λ_(max) = 380 nm CH₃ CH₃ OH CH₃ H

MC20 λ_(max) = 368 nm CH₃ CH₃ OH H H

MC21 CH₃ CH₃ —O—C₆H₅ H H —(CO)—CH₃ CN MC22 CH₃ CH₃ —O—CH₃ H H —(CO)—O—CH₃ CN MC23

—OC₂H₅ H

—(CO)OCH₃ MC24 R₂ + R₁; C₂H₅ —OC₂H₅ H — —(CO)OC₂H₅ —(CO)OC₂H₅

MC25 CH₃ CH₃

H —OC—O—C₂H₅ —CN MC26 CH₃ CH₃ Q + T: H H — —(CO)OC₂H₅

MC27 CH₃ CH₃ Q + R₁: H — —(CO)—C—CH₃ —CN

MC28 CH₃ CH₃ Q + R₁: H — —(CO)—O—CH₃ —SO₂—C₆H₅

MC29 CH₃ CH₃ —N(CH₃)₂ H H —(CO)—CH₃ —(CO)OC₂H₅ λ_(max) = 321 nm MC30 CH₃ CH₃ —N(CH₃)₂ H H —CN —(CO)—OCH₃ MC31 CH₃ CH₃ —N(CH₃)₂ H H —(CO)OC₂H₅ —(CO)OC₂H₅ λ_(max) = 321 nm MC32 CH₃ CH₃ —NH₂ H H —CN —(CO)OC₂H₅ MC33 CH₃ CH₃

H H —CN —(CO)OC₂H₅ MC34 CH₃ CH₃ R₆ + Q: H H —CN —(CO)OC₂H₅

MC35 CH₃ CH₃ R₆ + Q: H H —CN —(CO)OC₂H₅

MC36 R₂ + Q: CH₃ — H H —CN —(CO)OC₂H₅

MC37 R₂ + Q:

— H H —CN —(CO)OC₂H₅ MC38 R₂ + Q:

— H H —CN —(CO)OC₂H₅ MC39 R₂ + Q:

CH₃ — H H —CN

MC40 R₂ + Q:

— H H —CN —(CO)—O—C₂H₅ MC41 CH₃ CH₃ OH H H

MC42 CH₃ CH₃ Q + T H H — —(CO)—O—C₂H₅

MC43 R₂ + Q:

— H H —CN —(CO)—O—C₂H₅ MC44 R₂ + Q: CH₃ — H H —(CO)—O—C₂H₅ —(CO)—O—C₂H₅

MC45 λmax = 364 nm R₂ + Q:

— H H —CN —(CO)—O—C₂H₅ MC46 R₂ + Q: H — H H —CN —(CO)—O—C₂H₅

MC47 R₂ + Q:

— H H —CN

MC48 R₂ + Q:

— H H —CN —(CO)—O—C₂H₅ MC49 CH₃ CH₃ OH H H

MC50 CH₃ CH₃ CH₃ H H —COOCH₃ —COOCH₃ MC51 CH₃ CH₃ CH₃ H H —COOC₂H₅ —COOC₂H₅ MC52 CH₃ CH₃ CH₃ H H —COOC₃H₇-(n) —COOC₃H₇-(n) MC53 CH₃ CH₃ CH₃ H H —COOC₃H₇(i) —COOC₃H₇-(i) MC54 CH₃ CH₃ CH₃ H H —COOC₄H₉(n) —COOC₄H₉-(n) MC55 CH₃ CH₃ CH₃ H H —COOC₄H₉(t) —COOC₄H₉-(t) MC56 CH₃ CH₃ CH₃ H H —COOC₂H₅ —COOC₄H₉-(t) MC57 CH₃ CH₃ CH₃ H H —COOCH₃ —COOC₄H₉-(t) MC58 CH₃ CH₃ CH₃ H H —COOC₂H₅ —COOSi(CH₃)₃ MC59 CH₃ CH₃ CH₃ H H —COOSi(CH₃)₃ —COOSi(CH₃)₃ MC60 CH₃ CH₃ CH₃ H H —CO₂CH₂)₃Si(CH₃)₃ —CO₂(CH₂)₃Si(CH₃)₃ MC61 CH₃ CH₃ CH₃ H H —CONHC₂H₅ —CONHC₂H₅ MC62 CH₃ CH₃ CH₃ H H —CON(C₂H₅)₂ —CON(C₂H₅)₂ MC63 CH₃ CH₃ CH₃ H H CN CN MC64 CH₃ CH₃ CH₃ H H CN SO₂C₆H₆ MC65 CH₃ CH₃ CH₃ H H CN COOC₄H₉-(n) MC66 CH₃ CH₃ CH₃ H H CN COOC₈H₁₇-(i) MC67 CH₃ CH₃ CH₃ H H CN COOCH₃ MC68 CH₃ CH₃ CH₃ H H CN COOC₂H₅ MC69 CH₃ CH₃ CH₃ H H CN —CONHC₂H₅ MC70 CH₃ CH₃ CH₃ H H CN —CON(C₂H₅)₂ MC71 CH₃ CH₃ CH₃ H H SO₂C₆H₆ COOCH₃ MC72 CH₃ CH₃ CH₃ H H SO₂C₆H₆ COOC₂H₅ MC73 CH₃ CH₃ CH₃ H H SO₂C₆H₆ COOC₃H₇ MC74 CH₃ CH₃ CH₃ H H SO₂C₆H₆ COOC₄H₉ MC75 CH₃ CH₃ CH₃ H H SO₂C₆H₆ —COOC₈H₁₇(n) MC76 CH₃ CH₃ CH₃ H H SO₂C₆H₆ COOC₈H₁₇(i) MC77 CH₃ CH₃ CH₃ H H SO₂C₆H₆ —CONHC₂H₅ MC78 CH₃ CH₃ CH₃ H H SO₂tolyl COOC₂H₅ MC79 CH₃ CH₃ CH₃ H CH₃ —COOCH₃ —COOCH₃ MC80 CH₃ CH₃ CH₃ H CH₃ —COOC₂H₅ —COOC₂H₅ MC81 CH₃ CH₃ CH₃ H CH₃ —COOC₃H₇(n) —COO C₃H₉-(n) MC82 CH₃ CH₃ CH₃ H CH₃ —COOC₃H₇(i) —COO C₃H₇-(i) MC83 CH₃ CH₃ CH₃ H CH₃ —COO C₄H₉-(n) —COO C₄H₉(n) MC84 CH₃ CH₃ CH₃ H CH₃ —COO C₄H₉-(t) —COO C₄H₉(t) MC85 CH₃ CH₃ CH₃ H CH₃ —COO C₂H₅ —COOC₄H₉-(t) MC86 CH₃ CH₃ CH₃ H CH₃ —COOCH₃ —COOC₄H₉-(t) MC87 CH₃ CH₃ CH₃ H CH₃ —COOC₂H₅ —COOSi(CH₃)₃ MC88 CH₃ CH₃ CH₃ H CH₃ —COOSi(CH₃)₃ —COOSi(CH₃)₃ MC89 CH₃ CH₃ CH₃ H CH₃ —CONHC₂H₅ —CONHC₂H₅ MC90 CH₃ CH₃ CH₃ H CH₃ —CON(C₂H₅)₂ —CON(C₂H₅)₂ MC91 CH₃ CH₃ CH₃ H CH₃ CN CN MC92 CH₃ CH₃ CH₃ H CH₃ CN SO₂C₆H₆ MC93 CH₃ CH₃ CH₃ H CH₃ CN COOC₄H₉-(n) MC94 CH₃ CH₃ CH₃ H CH₃ CN COOC₈H₁₇-(i) MC95 CH₃ CH₃ CH₃ H CH₃ CN COOCH₃ MC96 CH₃ CH₃ CH₃ H CH₃ CN COOC₂H₅ MC97 CH₃ CH₃ CH₃ H CH₃ CN —CONHC₂H₅ MC98 CH₃ CH₃ CH₃ H CH₃ CN —CON(C₂H₅)₂ MC99 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ COOCH₃ MC100 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ COOC₂H₅ MC101 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ COOC₃H₇ MC102 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ COOC₄H₉ MC103 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ COOC₆H₁₇-(n) MC104 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ —COOC₈H₁₇-(i) MC105 CH₃ CH₃ CH₃ H CH₃ SO₂C₆H₆ —CONHC₂H₆ MC106 CH₃ CH₃ CH₃ H CH₃ SO₂tolyl COOC₂H₅ MC107 CH₃ CH₃ CH₃ H CH₃ SO₂tolyl —CONHC₂H₅ MC108 MC109 MC110 MC111 MC112 MC113

CH₃ CH₃ CH₃ CH₃ CH₃ CH₃ H H H H H H H H H H H H —COO C₂H₅ —COOSi(CH₃)₃ CN CN CN SO₂C₆H₆ —COO C₂H₅ —COOSi(CH₃)₃ CN SO₂O₆H₆ COOC₂H₅ COOCH₃ MC114 CH₃ H H SO₂tolyl COOC₂H₅ MC115 CH₃ H CH₃ —COO C₂H₅ —COO C₂H₆ MC116 CH₃ H CH₃ —COOSi(CH₃)₃ —COOSi(CH₃)₃ MC117 CH₃ H CH₃ CN CN MC118 CH₃ H CH₃ CN SO₂C₆H₆ MC119 CH₃ H CH₃ CN COOC₈H₁₇-(i) MC120 CH₃ H CH₃ SO₂C₆H₆ COOCH₃ MC121 MC122 MC123 MC124 MC125 MC126

CH₃ CH₃ CH₃ CH₃ CH₃ CH₃ H H H H H H H H H H H H —COOC₂H₅ —COOSi(CH₃)₃ CN CN CN SO₂C₆HD 6 —COOC₂H₅ —COOSi(CH₃)₃ CN SO₂C₆H₆ COOC₈H₁₇-(i) COOCH₃ MC127 CH₃ H CH₃ —COO C₂H₅ —COO C₂H₅ MC128 CH₃ H CH₃ —COOSi(CH₃)₃ —COOSi(CH₃)₃ MC129 CH₃ H CH₃ CN CN MC130 CH₃ H CH₃ CN SO₂C₆H₆ MC131 CH₃ H CH₃ CN COOC₆H₁₇(i) MC132 CH₃ H CH₃ SO₂C₆H₆ COOCH₃ MC133 CH₃ H CH₃ SO₂tolyl —CONHC₂H₅ MC134 i-propyl i-propyl CH₃ H H

MC135 CH₃ CH₃ CH₃ H H

MC136 CH₃ CH₃ CH₃ H H

MC137

CH₃ H H

MC138 R₂ + R₁:

CH₃ CH₃ H —

MC139 CH₃ H CH₃ H CH₃ -(CO)OCH₃ -(CO)OCH₃ MC140

H CH₃ H

MC141 CH₃ n-C₄H₉ CH₃ H CH₃ -(CO)—O—C₂H₅ -(CO)—O—C₂H₅ MC142 CH₃ CH₃ CH₃ H CH₃ -(CO)—O—Na -(CO)—O—Na MC143 R₂ + R₁: H CH₃ H — -(CO)—O—Na -(CO)—O—Na

MC144 CH₃ CH₃ H H CH₃

MC145 CH₃ CH₃ H

—CN -(CO)—CH₃ MC146 CH₃ CH₃ CH₃ H H

MC147

CH₃ H CH₃

-(CO)(CO)OC₂H₅ MC148 R₂ + R₁: CH₃ t-butyl H H -(CO)N(C₂H₅)₂ —CO—CH₃

MC149 i-propyl i-propyl

H —CN —CN MC150 CH₃ CH₃

H —CN —CN MC151 -(CH₂)₃—Si(CH₃)₃ CH₃ H H —CO—C(CH₃)₃ —CO—O—C₂H₅ MC152

H CH₃ H -(CO)OSi(CH₃)₃ -(CO)OSi(CH₃)₃ MC153 n-C₃H₇ CH₃ H H —CO—CH₃₃

MC154 CH₃ CH₃ C₂H₅ H H —NH(CO)C₅H₁₂ —CN MC155 C₂H₅ C₂H₆ CH₃ CH₃ CH₃ -(CO)—O—C₂H₅ -(CO)—O—C₂H₅ MC156 CH₃ CH₃

H CH₃ -(CO)—O—C₂H₅ -(CO)—O—C₂H₅ MC157 CH₃ CH₃ H

CH₃ -(CO)—O—C₂H₅ —CN MC158 CH₃ CH₃

H phenyl -(CO)—O—C₂H₅ -(CO)—O—C₂H₃ MC159 CH₃ CH₃ C₆H₅Br H CH₃ —CN -(CO)—O—C₂H₅ MC160 CH₃ CH₃ biphenyl H CH₃ CN -(CO)—O—C₂H₅ MC161 CH₃ CH₃

H CN -(CO)—O—C₂H₅ MC162 CH₃ CH₃ phenyl H CH₃ CN -(CO)—O—C₂H₅ MC163

CH₃ H H

CN -(CO)—O—C₂H₅ MC164 n-butyl n-butyl CH₃ H H -(CO)—O—C₂H₅ —SO₂—C₆H₅ MC165 CH₃ CH₃ H H phenyl -(CO)—CH₃

MC166 CH₃ CH₃ H H

-(CO)—CH₃ —CN MC167 CH₃ CH₃

H H -(CO)—O—CH₃ -(CO)—O—CH₃ MC168 CH₃ CH₃ H H phenyl —CN -(CO)OC(CH₃)₃ MC169 n-butyl n-butyl H H

—CN -(CO)OC(CH₃)₃ MC170 C₂H₅ C₂H₅ H H

—CN

MC171 CH₃ CH₃

H CH₃ —CN

MC172

H H

—CN

MC173 C₂H₅ C₂H₅ H H

—CN -(CO)—O—C₂H₅ MC174 CH₃ CH₃ H H —CN —CN -(CO)—O—CH₃ MC175 —C₂H₅OH —C₂H₅OH H H

—CN -(CO)—O—C₂H₅ MC176 H C₂H₅ H H

—CN -(CO)—O—C₂H₅ MC177 C₂H₅ n-butyl

H —CN —CN MC178 C₂H₅ C₂H₅ C₂H₅ H H (T = R₄)

MC179 C₂H₅OH C₂H₅OH CH₃ CH₃ H —CN

MC180 H

CH₃ H H

-(CO)CH₃ MC181

C₂H₅ H H —CN

MC182

C₂H₅ H H

MC183

MC184

MC185

MC186

MC187

MC188

MC189

MC190

MC191

MC192

MC193

MC194

MC195

MC196

MC197

MC198

The compounds of formula (1) are prepared according to known processes, as disclosed for example in J. Org. Chem. USSR (Engl. Transl.) 26(8), p. 1562f (1990); J. Heterocycl. Chem. 33(3), p. 763-766 (1996); Khimiya Geterotsiklicheskikh Soedinenii 11, p. 1537-1543 (1984); Khimiya Geterotsiklicheskikh Soedinenii 3, p. 397-404 (1982); Chem.Heterocycl.Comp. (Engl. Transl.) 24(8), 914-919 (1988).

The synthesis of the compounds used in the present invention is also disclosed in WO 0234710, Eur. J. Org. Chem. 2003, 2250-2253, J. Med. Chem. 1996, 39, 1112-1124 and J. Org. Chem., Vol. 37, No. 8, 1972, 1141-1145 as follows:

Vinylogerte CH-acid compounds are reacted with acetales of amides.

In J. Heterocyclic Chem., 27, 1990, 1143-1151 aminoacrylic acid esters or aminoacrylnitriles are reacted with ethoxymehtylenecyanoacetates in ethanol to the corresponding compounds used in the present invention.

In J. Prakt. Chem. 327 (1985) 4, 567-579 iminoformylation reactions are carried out on substituted crotonnitriles:

The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the micronized state.

The UV absorbers according to the present invention can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nano-scalar organic filters, particulate organic filters, UV-absorber pigments).

-   Any known process suitable for the preparation of microparticles can     be used for the preparation of the micronised UV absorbers, for     example wet-milling, wet-kneading, spray-drying from a suitable     solvent, by the expansion according to the RESS process (Rapid     Expansion of Supercritical Solutions) by reprecipitation from     suitable solvents.

The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.

A further object of the present invention is a UV absorber dispersion, comprising

-   (a) a micronised UV absorber of formula (1), each of them having a     particle size from 0.02 to 2 μm, and -   (b) a suitable dispersing agent.

The cosmetic formulations or pharmaceutical compositions according to the present invention may additionally contain one or more than one further conventional UV filter.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The compounds of formula (1) may also be used as as an anti-wrinkle perception modifier (see Example 29). This is a further object of the present invention.

Preferably, the following combinations comprising UV absorbers are of special interest;

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes:hydrocarbon oils: silicones or siloxanes (organosubstituted super-fatting agents, surfactants consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as spf enhancers,

Cosmetic or Pharmaceutical Preparations

Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:

-   -   skin-care preparations, e.g. skin-washing and cleansing         preparations in the form of tablet-form or liquid soaps,         soapless detergents or washing pastes,     -   bath preparations, e.g. liquid (foam baths, milks, shower         preparations) or solid bath preparations, e.g. bath cubes and         bath salts;     -   skin-care preparations, e.g. skin emulsions, multi-emulsions or         skin oils;     -   cosmetic personal care preparations, e.g. facial make-up in the         form of day creams or powder creams, face powder (loose or         pressed), rouge or cream make-up, eye-care preparations, e.g.         eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix         creams; lip-care preparations, e.g. lipsticks, lip gloss, lip         contour pencils, nail-care preparations, such as nail varnish,         nail varnish removers, nail hardeners or cuticle removers;     -   foot-care preparations, e.g. foot baths, foot powders, foot         creams or foot balsams, special deodorants and antiperspirants         or callus-removing preparations;     -   light-protective preparations, such as sun milks, lotions,         creams or oils, sunblocks or tropicals, pre-tanning preparations         or after-sun preparations;     -   skin-tanning preparations, e.g. self-tanning creams;     -   depigmenting preparations, e.g. preparations for bleaching the         skin or skin-lightening preparations;     -   insect-repellents, e.g. insect-repellent oils, lotions, sprays         or sticks;     -   deodorants, such as deodorant sprays, pump-action sprays,         deodorant gels, sticks or roll-ons;     -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;     -   preparations for cleansing and caring for blemished skin, e.g.         synthetic detergents (solid or liquid), peeling or scrub         preparations or peeling masks;     -   hair-removal preparations in chemical form (depilation), e.g.         hair-removing powders, liquid hair-removing preparations, cream-         or paste-form hair-removing preparations, hair-removing         preparations in gel form or aerosol foams;     -   shaving preparations, e.g. shaving soap, foaming shaving creams,         non-foaming shaving creams, foams and gels, preshave         preparations for dry shaving, aftershaves or aftershave lotions;     -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de         toilette, eau de parfum, parfum de toilette, perfume), perfume         oils or perfume creams;     -   cosmetic hair-treatment preparations, e.g. hair-washing         preparations in the form of shampoos and conditioners, hair-care         preparations, e.g. pretreatment preparations, hair tonics,         styling creams, styling gels, pomades, hair rinses, treatment         packs, intensive hair treatments, hair-structuring preparations,         e.g. hair-waving preparations for permanent waves (hot wave,         mild wave, cold wave), hair-straightening preparations, liquid         hair-setting preparations, hair foams, hairsprays, bleaching         preparations, e.g. hydrogen peroxide solutions, lightening         shampoos, bleaching creams, bleaching powders, bleaching pastes         or oils, temporary, semi-permanent or permanent hair colourants,         preparations containing self-oxidising dyes, or natural hair         colourants, such as henna or camomile.

Presentation Forms

The final formulations listed may exist in a wide variety of presentation forms, for example:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W         or PIT emulsion and all kinds of microemulsions,     -   in the form of a gel,     -   in the form of an oil, a cream, milk or lotion,     -   in the form of a powder, a lacquer, a tablet or make-up,     -   in the form of a stick,     -   in the form of a spray (spray with propellent gas or pump-action         spray) or an aerosol,     -   in the form of a foam, or     -   in the form of a paste.

Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.

Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.

Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.

The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.

PREPARATION EXAMPLES Example 1 Preparation of the Compound of Formula

A mixture of 8.58 g of dehydroacetic acid with 7.63 g of N,N-Dimethylformamid-dimethyl-acetate in 100 ml of tert.-butylmethylether is stirred for 8 hours at room temperature. Then the product is filtered off, washed with minor amounts of tert.-butylmethylether and dried in vacuum at 40° C.

The yield is nearly quantitative. Fp: 159-161° C.

Example 2 Preparation of Compound of Formula

A mixture of 1 g of 1-Ethoxycarbonyl-1-cyano-2-(N-dimethylaminomethylen)amino-4-dimethylaminobutadiene (prepared according to Chem. Heterocycl. Compd. (Engl. Transl.), 24, 8, 1988, 918) with 0.43 g of p-toluidine in 10 ml of dimethylformamide is boiled for 1 hour. The solvent is evaporated, the residue is ground in ether, filtered and dried in vacuum at 40° C. yielding 0.75 g of colorless crystals. Fp: 210-216° C.

Example 3 Preparation of the Compound of Formula

A mixture of 8.62 g pyrrolidine, 16.34 g malonic acid-cycl.-isopropylidene ester and 14.68 g acetylacetaldehyde dimethylacetal in 100 ml Toluene are stirred for 45 minutes at room temperature an kept under reflux for 67 hours.

The reaction mixture is stirred for 4 h at 3° C. and finally for 16 h at room temperture.

The raw product is filtered off and washed with diethylether and finally 4 times with 10 ml methanol.

After drying in vacuo at 60° C. 2.70 g of the product of formula (1) are obtained as bright-orange crystals.

λ_(max)=396 nm.

Example 4 Preparation of the Compound: of Formula

A mixture of 1.16 g of 1-Ethoxycarbonyl-1-cyano-2-(N-dimethylaminomethylen)amino-4-dimethylaminobutadiene (prepared according to Chem. Heterocycl. Compd. (Engl. Transi.), 24, 8, 1988, 918) with 0.47 g of aniline in 11 ml of acetic acid is boiled for 1 hour. After cooling to room temperature the product is filtered off, recrystallized from toluene/ethyl:acetate (1:1) yielding yellow crystals which were dried in vacuum at 40° C. The yield is 25%. λ_(max)=363 nm.

Application Examples Example 5 UV-A/UV-B Daily Care UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Oleth-3 Phosphate 0.60 Steareth-21 2.50 Steareth-2 1.00 Cetyl Alcohol 0.80 Stearyl Alcohol 1.50 Tribehenin 0.80 Isohexadecane 8.00 Ethylhexyl Methoxycinnamate 5.00 Part B Water qs to 100 Glycerin 2.00 UV-absorber as described in examples 1 to 4 3.00 Disodium EDTA 0.10 Part C Water 20.00  Diazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate Propylene Glycol 4.00 Part D Sodium Acrylates Copolymer (and) Paraffinium 1.50 Liquidum (and) PPG-1 Trideceth-6 Cyclopentasiloxane 4.50 PEG-12 Dimethicone 2.00 Tocopheryl Acetate 0.45 Water (and) Citric Acid qs Part E Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured into part B under continuous stirring. Immediately after the emulsification, Cyclopentasiloxane and PEG-12 Dimethicone from part D are incorporated into the mixture. Afterwards the mixture is homogenized with an Ultra Turrax at 11 000 rpm for 30 sec. After cooling down to 65° C. Sodium Acrylates Copolymer (and) Paraffinium Liquidum (and) PPG-1 Trideceth-6 are incorporated. Part C is added at a temperature <50° C. At a temperature ≦35° C. Tocopheryl Acetate is incorporated and subsequently the pH is adjusted with Water (and) Citric Acid. At room temperature part E is added.

Example 6 UV Day Lotion

% w/w INCI-Name (as supplied) Part A Cetyl Phosphate 1.75 C12-C15 Alkyl Benzoate 5.00 Cetearyl Alcohol/PEG-20 Stearate 2.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.50 Ethylhexyl Methoxycinnamate 3.00 Isononyl Isononanoate 2.00 Part B Aqua qs to 100 Xanthan Gum 0.35 UV-absorber as described in examples 1 to 4 5.00 Disodium EDTA 0.20 Propylene Glycol 2.00 Diazolidinyl Urea (and) Methylparaben (and) 0.70 Propylparaben (and) Propylene Glycol Glycerin 1.50 Part C Cyclopentasiloxane (and) Dimethiconol 1.00 Ethoxydiglycol 3.00 Dimethicone 2.00 Part D Triethanolamine qs

Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75° C. Part B is prepared and heated to 75° C. At this temperature part B is poured into part A under progressive stirring speed. Then the mixture is homogenized (30 sec., 15000 rpm). At a temperature <55° C. the ingredients of part C are incorporated. The mixture is cooled down under moderate stirring, then the pH is checked and adjusted with triethanolamine.

Example 7 Sun Protection Emulsion

% w/w INCI-Name (as supplied) Part A Cetearyl Alcohol (and) Dicetyl Phosphate10 4.00 (and) Ceteth-Phosphate C12-15 Alkyl Benzoate 2.00 Dicaprylyl Ether 3.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.00 Ethylhexyl Methoxycinnamate 3.00 Sodium Acrylates Copolymer (and) Glycine Soja 0.30 (and) PPG-1 Trideceth-6 Squalane 3.50 Part B Aqua qs to 100 UV-absorber as described in examples 1 to 4 5.00 Part C Diazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate Propylene Glycol 2.50 Aqua 10.00  Part D Cyclopentasiloxane, Dimethiconol 2.00 Ethoxydiglycol 5.00 Cyclopentasiloxane (and) Dimethicone/Vinyl- 2.00 dimethicone Crosspolymer Part E Sodium Hydroxide 0.10

Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75° C. Part B is prepared and heated to 75° C. At this temperature, part B is poured into part A under progressive stirring speed. Below 65° C. the ingredients of part D are added separately. After cooling down under moderate stirring to 55° C. part C is added. The pH is then checked and adjusted with sodium hydroxide. The mixture is homogenized for 30 sec at 16000 rpm.

Example 8 Every Day Lotion

% w/w INCI-Name (as supplied) Part A Stearyl Phosphate 5.00 Tricontanyl PVP 1.00 Ethoxydiglycol Oleate 3.00 Squalane 5.00 C12-15 Alkyl Benzoate 5.00 Ethylhexyl Methoxycinnamate 3.00 Glyceryl Stearate 2.00 Cetyl Alcohol 2.00 Part B Aqua 20.00  UV-absorber as described in examples 1 to 4 3.00 Part C Aqua qs to 100 Steareth-10 Allyl Ether/Acrylates Copolymer 0.50 Glycerin 2.50 Diazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate Sodium Lauroyl Glutamate 0.70 Part D Cyclopentasiloxane (and) Dimethiconol 1.50 Triethanolamine 1.85

Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75° C. Part C is prepared and heated to 75° C. Part C is poured into the part A under moderate stirring. Immediately after the emulsification part B is added, then neutralized with a part of the triethanolamine. The mixture is homogenized for 30 sec. After cooling down under moderate stirring Cyclopentasiloxane (and) Dimethiconol are added. Below 35° C. the pH is checked and adjusted with triethanolamine.

Example 9 Sprayable Sunscreen Emulsion

% w/w INCI-Name (as supplied) Part A Ceteareth-15 (and) Glyceryl Stearate 3.00 Stearyl Alcohol 1.00 Cetyl Ricinoleate 0.80 Dicaprylyl Ether 3.00 C12-15 Alkyl Benzoate 3.00 Isohexadecane 2.50 Stearyl Dimethicone 1.00 Ethylhexyl Methoxycinnamate 4.00 Cetyl Alcohol 0.80 Di-C12-13 Alkyl Tartrate 3.00 Part B Aqua qs to 100 Steareth-10 Allyl Ether/Acrylates 0.45 Copolymer PEG-7 Glyceryl Cocoate 2.50 Glycerin 2.00 Propylene Glycol 3.00 Part C Diazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate Aqua 20.00  UV-absorber as described in examples 12.00  1 to 4 Titanium Dioxide (and) Silica (and) 8.00 Sodium Polyacrylate Part D Cyclopentasiloxane (and) Dimethiconol 0.85 Part E Sodium Hydroxide (and) Water qs to pH 6.50-7.00 Part F Fragrance qs

Manufacturing Instruction

Part A and part B are heated up to 80° C. Part A is blended into part B under stirring and homogenized with an UltraTurrax at 11 000 rpm for 30 sec. Part C is heated to 60° C. and added slowly to the emulsion. After cooling down to 40° C. part D is incorporated at room temperature and part E is added.

Example 10 Daily Care Lotion

% w/w INCI-Name (as supplied) Part A Polyglyceryl Methyl Glucose Distearate 2.50 Cetearyl Alcohol 2.00 Octyl Stearate 3.00 Caprylic/Capric Triglyceride 4.00 Isohexadecane 4.00 Ethylhexyl Methoxycinnamate 2.70 Part B Aqua 64.80 Glycerin 5.00 Phenoxyethanol (and) Methylparaben (and) 0.50 Butylparaben (and) Ethylparaben (and) Propylparaben UV-absorber as described in examples 1 to 4 8.00 Part C Cyclomethicone (and) Dimethicone 3.00 Part D Steareth-10 Allyl Ether/Acrylates Copolymer 0.50

Manufacturing Instruction

Part A and B are heated to 75° C. Part A is added into part B under continuous stirring and homogenized with 11000 rpm for 1 minute. After cooling down to 50° C. part C is added under continuous stirring. After cooling further down to 30° C. part D is added. Afterwards the pH is adjusted between 6.00-6.50.

Example 11 Daily Care with UV Protection

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate SE 3.00 Glyceryl Stearate and PEG-100 Stearate 3.50 Cetyl Alcohol 1.50 Myristyl Myristate 2.00 Isopropyl Palmitate 2.50 Paraffinum Perliquidum 5.00 Octyl Dimethyl PABA 3.00 Part B Aqua qs to 100 Propylene Glycol 7.50 Phenoxyethanol (and) Methylparaben (and) 1.00 Butylparaben (and) Ethylparaben (and) Propylparaben Part C Aqua 30.00  UV-absorber as described in examples 1 to 4 10.00  Part D Sodium Acrylates Copolymer (and) Paraffinium 2.00 Liquidum (and) PPG-1 Trideceth-6 Part E Citric Acid 0.30

Manufacturing Instruction:

Part A and B are heated separately to 75° C. After adding part B into part A the mixture is homogenized with Ultra Turrax for one minute at 11000 rpm. After cooling down to 50° C. part C is added. Afterwards the mixture is homogenized for one minute at 16000 rpm. At a temperature <40° C. part D is added. At room temperature the pH-value is adjusted with part E between 6.00 and 6.50.

Example 12 O/W Every Day UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100 Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00 C12-15 Alkyl Benzoate 5.00 Isopropyl Palmitate 5.00 Ethylhexyl Methoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50 Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described in examples 8.00 1 to 4 Part D Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part E Water (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and B are heated separately up to 75° C., part C is heated to 60° C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part C is incorporated. After cooling down to 40° C. part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.

Example 13 O/W Every Day UV Protection

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100 Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00 C12-15 Alkyl Benzoate 5.00 Isopropyl Palmitate 5.00 Ethylhexyl Methoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50 Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described in examples 8.00 1 to 4 Part D Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part E Water (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and B are heated separately up to 75° C., part C is heated to 60° C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part C is incorporated. After cooling down to 40° C. part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.

Example 14 Sunscreen Cream

% w/w INCI-Name (as supplied) Part A Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.50 Ceteth-10 Phosphate C12-15 Alkyl Benzoate 6.00 Caprylic/Capric Triglyceride 7.00 Pentaerythritol Tetraisostearate 2.00 Ethylhexyl Methoxycinnamate 3.00 Isoamyl p-Methoxycinnamate 2.00 Part B Aqua qs to 100 Glycerin 2.00 Propylene Glycol 1.50 Magnesium Aluminium Silicate 1.20 Part C Steareth-10 Allyl Ether/Acrylates Copolymer 0.50 UV-absorber dispersion as described in examples 12.00  1 to 4 Part D Phenyl Trimethicone 1.50 Phenoxyethanol (and) Methylparaben (and) 0.70 Butylparaben (and) Ethylparaben (and) Propylparaben Part E Sodium Hydroxide 0.90

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part B is added into part A under continuous stirring and afterwards homogenized with Ultra Turrax for 30 sec at 11000 rpm. After cooling down to 60° C. part C is added. At 40° C. part C is added and homogenized for 15 sec at 11000 rpm. At room temperature the pH-value is adjusted with part E.

Example 15 UVA/UVB Daily Care Lotion, type O/W

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100 Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Mineral Oil 15.00  Part B Water qs to 100 Polysorbate 60 0.50 Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described in examples 8.00 1 to 4 Part D Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part E Water (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and B are heated separately to 75° C.; part C to 60° C. Part B is poured into part A under stirring. After one-minute of homogenization at 11000 rpm part C is added to the mixture of NB. After cooling down to 40° C. part D is incorporated. At room temperature the pH value is adjusted with part E between 6.3 and 7.0. Finally part F is added.

Example 16 UVA/UVB Daily Care Lotion, Type O/W

% w/w INCI-Name (as supplied) Part A Oleth-3 Phosphate 0.60 Steareth-21 2.50 Steareth-2 1.00 Cetyl Alcohol 0.80 Stearyl Alcohol 1.50 Tribehenin 0.80 Isohexadecane 8.00 Part B Water qs to 100 Glycerin 2.00 Disodium EDTA 0.10 Part C Cyclopentasiloxane 4.50 PEG-12 Dimethicone 2.00 Part D Sodium Acrylates Copolymer (and) Mineral Oil 1.50 (and) PPG-1 Trideceth-6 Part E UV-absorber dispersion as described in examples 10.00  1 to 4 Part F Tocopheryl Acetate 0.45 DMDM Hydantoin (and) Iodopropynyl 0.85 Butylcarbamate (and) Aqua (and) Butylene Glycol Part G Water (and) Citric Acid qs Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured into part B under stirring. Immediately after the emulsification, part C is added to the mixture and homogenized with an Ultra Turrax at 11000 rpm for 30 sec. After cooling down to 65° C. Sodium Acrylates Copolymer (and) Mineral Oil (and) PPG-1 Trideceth-6 At 50° C. is added slowly to the UV absorber dispersion. At about 35-30° C. part F is incorporated. The pH is adjusted with part G between 5.5 and 6.5.

Example 17 UV-A/UV-B Every Day Protection Lotion O/W

% w/w INCI-Name (as supplied) Part A Glyceryl Dilaurate 2.00 Ethylhexyl Palmitate 6.00 Cetyl Alcohol 1.00 Glyceryl Stearate 2.00 Laureth-23 1.00 Isopropyl Palmitate 2.00 Tribehenin 0.80 Beeswax 1.50 Lanolin Oil 1.00 Part B Water qs to 100 Propylene Glycol 4.00 Water (and) Titanium Dioxide (and) Alumina 4.00 (and) Sodium Meta-phosphate (and) Phenoxyethanol (and) Sodium Methylparaben Part C Steareth-10 Allyl Ether/Acrylates Copolymer 1.00 Part D Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben UV-absorber dispersion as described in examples 8.00 1 to 4 Part E Water (and) Sodium Hydroxide qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part A is poured into part B while stirring and homogenized with an Ultra Turrax by 11000 rpm for 30 sec. After cooling down to 60° C. part C is incorporated. At 40° C. part D is added slowly under continuous stirring. The pH is adjusted with part E between 6.50-7.00.

Example 18 Sprayable Sunscreen Lotion

% w/w INCI-Name (as supplied) Part A Potassium Cetyl Phosphate 0.20 Isohexadecane 7.00 VP/Eicosene Copolymer 1.50 Di-C12-13 Alkyl Tartrate 6.00 Ethylhexyl Triazone 2.50 C12-15 Alkyl Benzoate 4.50 Part B Water qs to 100 Sorbeth-30 2.00 Sorbitan Stearate (and) Sucrose Cocoate 4.00 Titanium Dioxide (and) Alumina (and) Silica 2.50 (and) Sodium Polyacrylate Part C Water 30.00  UV-absorber dispersion as described in examples 12.00  1 to 4 Part D Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part E Water (and) Citric Acid qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C., part C is heated to 50° C. Part B is poured into part A and homogenized with an Ultra Turrax for 1 minute at 11000 rpm. After cooling down to 50° C. part C is added under continuous stirring. At 40° C. part D is incorporated and homogenized again for 10 sec. at 11000 rpm. The pH is adjusted with part E.

Example 19 O/W Every Day UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100 Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00 Caprylic/Capric Triglyceride 5.00 Isopropyl Palmitate 5.00 Ethylhexyl Methoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50 Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described in examples 8.00 1 to 4 Part D Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part E Water (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately up to 75° C., part C is heated to 60° C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part C is incorporated. After cooling down to 40° C. part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.

Example 20 Water Resistant Sunscreen Emulsion

% w/w INCI-Name (as supplied) Part A Polyglyceryl-10 Pentastearate (and) Behenyl 2.50 Alcohol (and) Sodium Stearoyl Lactylate VP/Eicosene Copolymer 1.50 Stearyl Alcohol 1.50 Squalane 4.00 C12-15 Alkyl Benzoate 7.50 Octocrylene 1.50 4-Methylbenzylidene Camphor 3.00 Ethylhexyl Methoxycinnamate 2.00 Part B Water qs to 100 Glycerin 1.80 Steareth-10 Allyl Ether/Acrylates Copolymer 0.80 Part C UV-absorber dispersion as described in examples 9.00 1 to 4 Part D VP/Hexadecene Copolymer 2.70 Cyclomethicone 1.50 Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part E Aqua (and) Tocopheryl Acetate (and) Caprylic/ 3.50 Capric Triglyceride (and) Polysorbate 80 (and) Lecithin Part F Fragrance qs Water (and) Sodium Hydroxide qs

Manufacturing Instruction:

Part A and part B are heated separately to 80° C. Part A is poured into part B under continuous stirring. Afterwards the mixture is homogenized with an Ultra Turrax at 11 000 rpm for 1 min. After cooling down to 60° C. part C is incorporated. At 40° C. part D is added and the mixture homogenized for a short time again. At 35° C. part E is added and at room temperature Fragrance is added. Finally the pH is adjusted with Sodium Hydroxide.

Example 21 UVA/UVB Sun Protection Lotion, O/W Type

% w/w INCI-Name (as supplied) Part A Potassium Cetyl Phosphate 2.00 Tricontanyl PVP 1.00 Caprylic/Capric Triglyceride 5.00 C12-15 Alkyl Benzoate 5.00 Cetearyl Isononanoate 5.00 Glyceryl Stearate 3.00 Cetyl Alcohol 1.00 Dimethicone 0.10 Ethylhexyl Methoxycinnamate 5.00 Part B Water qs to 100 Glycerin 3.00 Part C Steareth-10 Allyl Ether/Acrylates Copolymer 0.50 Part D UV-absorber dispersion as described in 8.00 examples 1 to 4 Part E Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part F Water (and) Sodium Hydroxide qs to pH 7.00 Part G Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part B is poured into part A under moderate stirring. The mixture is homogenized with an Ultra Turrax at 11000 rpm for 1 minute. After cooling down to 70° C. part C is added under stirring. After cooling further down to 50° C. part D is incorporated very slowly. At 40° C. part E is added. At room temperature the pH is adjusted with part F to 7.00 and part G is added.

Example 22 UVA/UVB Sun Protection Lotion, O/W Type

% w/w INCI-Name (as supplied) Part A Potassium Cetyl Phosphate 2.00 Tricontanyl PVP 1.00 Caprylic/Capric Triglyceride 5.00 C12-15 Alkyl Benzoate 5.00 Cetearyl Isononanoate 5.00 Glyceryl Stearate 3.00 Cetyl Alcohol 1.00 Dimethicone 0.10 Ethylhexyl Methoxycinnamate 5.00 Part B Water qs to 100 Glycerin 3.00 Part C Steareth-10 Allyl Ether/Acrylates Copolymer 0.50 Part D UV-absorber dispersion as described in 20.00  examples 1 to 4 Part E Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part F Water (and) Sodium Hydroxide qs to pH 7.00 Part G Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part B is poured into part A under moderate stirring. The mixture is homogenized with an Ultra Turrax at 11000 rpm for 1 minute, After cooling down to 70° C. add part C is added under stirring. After cooling further down to 50° C. part D is incorporated very slowly. At 40° C. part E is added. At room temperature the pH is adjusted with part F to 7.00 and part G is added.

Example 23 Sunscreen Lotion

% w/w INCI-Name (as supplied) Part A Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.00 Ceteth-10 Phosphate C12-15 Alkyl Benzoate 2.00 Dicaprylyl Ether 3.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.00 Ethylhexyl Methoxycinnamate 3.00 Sodium Acrylates Copolymer (and) Glycine Soja 0.30 (and) PPG-1 Trideceth-6 Squalane 3.50 VP/Eicosene Copolymer 2.00 Part B Water qs to 100 UV-absorber dispersion as described in examples 5.00 1 to 4 Part C Diazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate Propylene Glycol 2.50 Water 10.00  Part D Cyclopentasiloxane (and) Dimethiconol 2.00 Ethoxydiglycol 5.00 Cyclopentasiloxane (and) Dimethicone/Vinyl 2.00 Dimethicone Crosspolymer Part E Aqua (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction

Part A and part B are heated separately up to 75° C. Part B is poured into part A under progressive stirring speed. At a temperature <65° C. the ingredients of part D are added separately. After cooling down to 55° C. under moderate stirring part C is added. At a temperature <35° C. the pH is checked and adjusted with Sodium Hydroxide and homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm. Part F is added at room temperature.

Example 24 W/O Sunscreen Lotion

% w/w INCI-Name (as supplied) Part A PEG-7 Hydrogenated Castor Oil 3.00 Polyglyceryl-3 Diisostearate 4.00 Microcrystalline Wax 1.00 Magnesium Stearate 1.50 Propylparaben 0.10 Mineral Oil 15.00  Octyldodecanol 8.00 Ethylhexyl Triazone 1.00 Ethylhexyl Methoxycinnamate 2.00 Part B Water qs to 100 Water (and) Citric Acid 0.05 Methylparaben 0.15 Magnesium Sulfate 0.50 Part C UV-absorber dispersion as described in example 9.00 1 or 2 Fragrance qs

Manufacturing Instruction:

Part A is heated to 80° C. whilst stirring. Part B is added into part A and homogenized with an Ultra Turrax at 11 000 rpm for one minute. After cooling down to 30° C. part C is incorporated.

Example 25 Skin Protection Sunscreen Lotion W/O

% w/w INCI-Name (as supplied) Part A Polyglyceryl-2 Dipolyhydroxystearate 3.00 Glyceryl Oleate 3.00 Cetearyl Isononanoate 7.00 Hexyl Laurate 6.00 Dicaprylyl Ether 6.00 Propylparaben 0.10 Hexyldecanol 3.00 Magnesium Stearate 1.00 Beeswax 1.00 Ethylhexyl Methoxycinnamate 4.00 Part B Water qs to 100 Methylparaben 0.15 Magnesium Sulfate 1.00 Part C UV-absorber dispersion as described in examples 6.00 1 to 4

Manufacturing Instruction:

Part A is heated separately to 80° C. under gentle stirring. Part B is added to part A and homogenized for one minute at 11000 rpm. After cooling down to 30° C. part C is added under continuous stirring.

Example 26 O/W emulsion

% w/w INCI-Name (as supplied) Part A UV absorber of formula (MC 14) 3 g sesame oil 10 g glyceryl stearate 4 g stearic acid 1 g cetyl alcohol 0.5 g polysorbate 20 0.2 g Part B propylene glycol 4 g propylparaben 0.05 g methylparaben 0.15 g triethanolamine 0.1 g carbomer 934 0.1 g water ad 100 ml

Preparation of the Emulsion Phase (A):

Firstly, the UV absorber is dissolved in sesame oil. The other components of (A) are added thereto and combined.

Phase (B):

Propylparaben and methylparaben are dissolved in propylene glycol. 60 ml of water are then added, heating to 70° C. is carried out and then carbomer 934 is emulsified therein.

Emulsion:

(A) is slowly added to (B) with vigorous application of mechanical energy. The volume is adjusted to 100 ml by the addition of water.

Example 27 Daily Care Cream, Type O/W

% w/w INCI name (as used) Part A Glyceryl stearate (and) cetearyl alcohol (and) cetyl 4.0 palmitate (and) cocoglycerides Ceteareth-12 4.0 Cetearyl alcohol 2.0 Dicaprylyl ether 4.5 Ethylhexyl stearate 4.0 Hexyl laurate 3.5 Ethylhexyl triazone 1.0 Benzylidene malonate polysiloxane 2.0 HDI/trimethylol hexyl-lactone crosspolymer (and) 5.0 silica Stearyl dimethicone 1.0 Dimethicone 2.0 Cetyl alcohol 0.8 compound of formula (MC 14) 2.0 Part B Water q.s. to 100 Water (and) scleroglucan (and) phenoxyethanol 2.0 Glycerol 2.0 Part C Steareth-10 allyl ether/acrylate copolymer  0.45 Phenoxyethanol (and) methylparaben (and) 0.7 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Aqua (and) tocopheryl acetate (and) caprylic/capric 4.0 triglyceride (and) polysorbate 80 (and) lecithin Part E Water (and) sodium hydroxide q.s. Fragrance q.s.

Preparation Procedure:

Part A and part B are heated separately to 80° C. Part A is poured into part B, whilst stirring continuously. Afterwards the mixture is homogenized with an Ultra Turrax at 11 000 rpm for 20 sec. The mixture is cooled to 60° C. and part C is added. At a temperature below 30° C., part D is added and the pH value is adjusted with sodium hydroxide to between 6.5 and 7.0. Finally, fragrance is added.

Example 28 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 compound of formula (MC 14) 2.0 Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s.

Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. The mixture is cooled to 60° C. and part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm) and further cooled, with moderate stirring. At room temperature, the pH is adjusted with sodium hydroxide solution to between 5.5 and 6.0. Finally, fragrance is added.

Example 29 Daily Care UV-Protection Lotion

% w/w INCI name (as used) Part A Oleth-3 phosphate 0.6 Steareth-21 2.5 Steareth-2 1.0 Cetyl alcohol 0.8 Stearyl alcohol 1.5 Tribehenin 0.8 Isohexadecane 8.0 compound of formula (MC 14) 5.0 Part B Water q.s. to 100 Glycerol 2.0 Methylene bis-benzotriazolyl tetramethylbutylphenol 3.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Disodium EDTA 0.1 Part C Water 20.0  Diazolidinyl urea (and) iodopropynyl  0.15 butylcarbamate Propylene glycol 4.0 Part D Sodium acrylate copolymer (and) liquid paraffin 1.5 (and) PPG-1 trideceth-6 Cyclopentasiloxane 4.5 PEG-12 dimethicone 2.0 Tocopheryl acetate  0.45 Water (and) citric acid q.s. Part E Fragrance q.s.

Preparation Procedure

Heat part A and part B separately to 75° C. Pour part A into part B, whilst stirring continuously. Immediately after emulsification, incorporate in the mixture SF 1202 and SF 1288 from part D. Afterwards homogenise with an Ultra Turrax at 11 000 rpm for 30 sec. Allow to cool to 65° C. and incorporate SALCARE® SC91. At a temperature below 50° C., add part C. At 35° C. or below, incorporate vitamin E acetate and subsequently adjust the pH with citric acid. At room temperature, add part E.

Example 30 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 compound of formula (MC 14) 2.0 Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s.

Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. The mixture is cooled to 60° C., and part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm). After further cooling, with moderate stirring, the pH is adjusted with sodium hydroxide at room temperature. A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance is added.

Example 31 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 Mixture of the compound of formula (MC 14) 2.0 (50%) and Uvinul A Plus CAS Reg. No. 302776-68-7 (50%) Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s.

Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. After cooling 60° C., part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm). After further cooling, with moderate stirring, the pH is adjusted at room temperature with sodium hydroxide solution to between 5.50 and 6.00. Finally, fragrance is added.

Example 32 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate 2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/capric triglyceride 6.5 Mixture of compound of formula (MC 14) 2.0 (50%) and benzylidene camphor, CAS Reg. No. 36861-47-9 (50%) Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and) isobutylparaben Part D Methylene bis-benzotriazolyl tetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and) propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodium hydroxide q.s. Fragrance q.s.

Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11 000 rpm for 15 sec. After cooling to 60° C., part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11 000 rpm). After further cooling, with moderate stirring, the pH is adjusted at room temperature with sodium hydroxide. A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance is added. 

1. A cosmetic or pharmaceutical preparation comprising at least one compound of formula (1) together with cosmetically tolerable carriers or adjuvants

wherein Q is hydrogen; C₁-C₂₂alkyl; —OH; —OR₇; —NR₇R₈; or —N═R₉; R₁ is hydrogen; C₁-C₂₂alkyl; —OR₇, —SR₇; —NR₇R₈; C₁-C₂₂alkyl; C₂-C₁₂ alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; C₇-C₁₂aralkyl; C₁-C₁₂heteroalkyl, C₂-C₁₁heteroaralkyl; C₆-C₁₀aryl; or C₁-C₉heteroaryl; R₄ is cyano; COR₇, COOR₇; CONR₇R₈; SO₂(C₆-C₁₂)aryl; C₂-C₁₂alk-1-enyl; C₃-C₁₂cycloalk-1-enyl; C₂-C₁₂alk-1-inyl; C₂-C₁₂heteroalkyl; C₃-C₅heterocycloalkyl; C₆-C₁₀aryl; or C₁-C₉heteroaryl; R₅ is —COR₇; —COOR₇; —OR₇; —SR₇, —NHR₇, —NR₇R₈; C₁-C₂₂alkyl; C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; C₇-C₁₂aralkyl; C₁-C₁₂alkylphenyl; C₁-C₁₂alkoxy-C₆-C₁₀aryl; C₁-C₁₂heteroalkyl; C₂-C₁₁heteroaralkyl; C₃-C₁₂cycloheteroalkyl; C₆-C₁₀aryl; C₁-C₁₂alkoxy-C₆-C₁₀aryl; or C₁-C₉heteroaryl; R₆ is hydrogen; C₁-C₂₂alkyl; C₁-C₂₂alkoxy; or COR₇, R₇ and R₈ independently from each other are hydrogen; C₁-C₂₂alkyl; C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl; C₃-C₁₂cycloalkenyl; —(CH₂)_(t)COOH; C₇-C₁₂aralkyl; C₁-C₁₂heteroalkyl; C₂-C₁₁heteroaralkyl; C₆-C₁₀aryl; C₁-C₉heteroaryl; Si—R₁₀R₁₁R₁₂; Si(OR₁₀)(OR₁₁)(OR₁₂); SiR₁₀(OR₁₁)(OR₁₂); SiR₁₀R₁₁(OR₁₂); —(CH₂)_(u)—O—(CH₂)_(v)—SiR₁₀R₁₁R₁₂; or a radical X-Sil; t, u and v, independently from each other are a number from 1 to 5; R₉ is a (C₁-C₆)alkylidene radical; R₁₀, R₁₁, R₁₂ independently form each other are C₁-C₂₂alkyl; X is a linker; Sil is a silane-, oligosiloxane- or polysiloxane radical; R₁ and R₂, R₁ and Q, R₁ and R₆, R₁ and T, R₂ and R₃, R₂ and R₄, R₂ and R₆, R₂ and Q, R₄ and R₆, R₄ and T, R₆ and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N—, O- and/or S-heterocyclic rings, and each N atom in a N-heterocyclic ring may be substituted by C₁-C₂₂alkyl; n is a number from 1 to 4; wherein at least one of the radicals R₁, R₆ or Q is different from hydrogen; if n=1 T is —COR₅; —CN; C₆-C₁₀aryl; —NHR₅; or —SO₂—(C₆-C₁₂)aryl; R₂ and R₃ independently from each other are C₁-C₂₂alkyl; hydroxy-C₁-C₂₂alkyl; C₂-C₁₂alkenyl; C₂-C₁₂alkinyl; C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkenyl; C₇-C₁₂ aralkyl; C₁-C₁₂heteroalkyl; C₃-C₁₂cycloheteroalkyl; C₆-C₁₀aryl; C₁-C₉heteroaryl; or a radical of formula

p is a number from 5 to 100 q is a number from 1 to 5; s is a number from 0 to 4; if n=2 R₂ and R₃ are each C₁-C₅alkylene; and simultaneously T is defined as for n=1; or T is a bivalent radical of formula —NR₇—V—NR₇—, wherein V is phenylene; or C₁-C₅alkylene; R₇ is hydrogen; or C₁-C₅alkyl; and R₂ and R₃ simultaneously are defined as for n=1; if n=3 one of R₂, R₃ or T is a trivalent radical; if n=4 one of R₂, R₃ or T is a tetravalent radical; for protecting of human hair and skin against the damaging effect of UV radiation.
 2. The cosmetic or pharmaceutical preparation according to claim 1 wherein the compound of formula (1) is present in the preparation in the micronized state.
 3. The cosmetic or pharmaceutical preparation according to claim 2 wherein the compound of formula (1) is present in a UV absorber dispersion, comprising (a) at least one micronised UV absorber of formula (1), each of them having a particle size from 0.02 to 2 μm, and (b) a suitable dispersing agent.
 4. The cosmetic or pharmaceutical preparation according to claim 1 wherein said preparation is selected from the group consisting of anti-wrinkle perception modifiers, skincare preparations, bath preparations, cosmetic personal care preparations, eye-care preparations, lip-care preparations, nail-care preparations, foot-care preparations, light-protective preparations, skin-tanning preparations, depigmenting preparations, insect repellents, deodorants, antipersirants, hair removal preparations, shaving preparations, fragrance preparations, and cosmetic hair-treatment preparation.
 5. The cosmetic or pharmaceutical preparation according to claim 1 wherein said preparation is selected from the group consisting of creams, gels, lotions, alcoholic and aqueous solutions, alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders and ointments. 